1、Designation: C1771 13Standard Test Method forDetermination of Boron, Silicon, and Technetium inHydrolyzed Uranium Hexafluoride by Inductively CoupledPlasmaMass Spectrometer After Removal of Uranium bySolid Phase Extraction1This standard is issued under the fixed designation C1771; the number immedia
2、tely following the designation indicates the year oforiginal adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.1. Scope1.1 This te
3、st method covers the determination of boron,silicon and technetium in hydrolyzed uranium hexafluoride(UF6) by Inductively Coupled Plasma Mass Spectrometry(ICP-MS) after separation of the uranium by solid phaseextraction.1.2 The values stated in SI units are to be regarded asstandard. No other units
4、of measurement are included in thisstandard.1.3 This standard does not purport to address all of thesafety concerns, if any, associated with its use. It is theresponsibility of the user of this standard to establish appro-priate safety and health practices and determine the applica-bility of regulat
5、ory limitations prior to use. Some specifichazards statements are given in Section 7 on Hazards.2. Referenced Documents2.1 ASTM Standards:2C787 Specification for Uranium Hexafluoride for Enrich-mentC859 Terminology Relating to Nuclear MaterialsC996 Specification for Uranium Hexafluoride Enriched toL
6、ess Than 5 %235UC1346 Practice for Dissolution of UF6from P-10 Tubes,C1689 Practice for Subsampling of Uranium HexafluorideD1193 Specification for Reagent Water3. Terminology3.1 DefinitionsFor definitions of other standard terms inthis test method, refer to Terminology C859.3.2 Definitions:3.2.1 int
7、ernal reference solution, na solution containingnon-analyte elements, the signal from which is used to correctfor variation in the performance of a measuring instrumentthrough the course of analyzing a batch of samples, therebyimproving precision.3.2.2 method blank, na solution which in so far as is
8、practical duplicates the sample to be analyzed and passesthrough the same measurement process but does not initiallycontain significant quantities of any of the analytes to bemeasured.3.2.2.1 DiscussionThe method blank does not initiallycontain significant quantities of analyte, hence the value of a
9、nyanalyte measured may be assumed to be due to interference,matrix effects or contamination introduced as a consequence ofsample processing, The contribution of such factors to thevalue measured on the genuine sample may therefore beeliminated by subtracting the measured value for the methodblank, t
10、ypically providing a better estimate for the true value ofthe quantity of analyte in the sample.3.2.3 recovery correction, na factor applied to the mea-sured value of the analyte in the sample to account for lossesof analyte during sample processing.3.2.3.1 DiscussionSome of the analyte originally p
11、resentin a sample is likely to be lost during the process of preparingthe sample for instrumental measurement, so that the measuredvalue will typically be subject to negative bias. The proportionof analyte lost may be estimated by repeated measurement ofa sample containing a known quantity of the an
12、alyte and acorrection factor introduced to account for losses. Recoverycorrection is only required when analyte losses are significantwhen compared with overall measurement uncertainty.3.2.4 spike, na known quantity of analyte added to asample.4. Summary of Test Method4.1 A 4 % by weight solution of
13、 UF6is initially prepared byreacting a quantity of UF6with water. Sub-sampling of UF6may be carried out as described in Practice C1689. Preparation1This test method is under the jurisdiction of ASTM Committee C26 on NuclearFuel Cycle and is the direct responsibility of Subcommittee C26.05 on Methods
14、 ofTest.Current edition approved Jan. 1, 2013. Published February 2013. DOI: 10.1520/C1771-132For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document
15、Summary page onthe ASTM website.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States1of the hydrolyzed solution may be carried out as described inPractice C1346. The laboratory may choose to adopt a simpli-fied version of the standard prac
16、tices, or to adopt otherpractices, provided that any additional error thereby introducedis incorporated within precision statements for the method.4.2 Concentrated nitric acid is added to the uranium solutionto give a nitric acid concentration of approximately 1.5 M. Thesolution is then passed throu
17、gh a diamyl amylphosphonate(DAAP) resin column which retains the uranium. Boron,silicon and technetium are eluted from the column with 2 Mnitric acid and the solution made up to volume with reagentwater. The boron, silicon and technetium concentrations arethen measured using an ICP-MS. An on-line in
18、ternal referencesolution may be used to correct results for any instrumentaldrift and results are blank corrected using a prepared methodblank.NOTE 1The method described in this standard usesa3mLsample of4 % by weight UF6solution. The apparatus and the quantities andconcentrations of reagents and ma
19、terials described in the standard areappropriate to this sample size and concentration. The data presented inSection 14 have been generated using samples of this size and concen-tration. Alternative sample sizes and concentrations may be used but willrequire that the laboratory adjust apparatus, rea
20、gents and materialsaccordingly and validate the method for the adjusted conditions.5. Significance and Use5.1 This method is capable of measuring the concentrationof boron, silicon and technetium in UF6. Limits for thesecontaminants are set in Specifications C787 and C996.6. Interferences6.199Tc suf
21、fers an isobaric interference with99Ru and amolecular interference due to98MoH+ions; however, thediluted, hydrolyzed UF6samples should not give rise to anysignificant amount of99Ru or98MoH+ions.7. Apparatus7.1 Ordinary laboratory apparatus are not listed but areassumed to be present.7.1.1 ICP-MS con
22、trolled by computer and fitted with asso-ciated software and peripherals, including an inert sampleintroduction system.NOTE 2A standard quartz sample introduction system is not suitableas it will affect the silicon measurement. A perfluoroalkoxy fluorocarbonplastic (PFA) introduction system with pla
23、tinum injector has provenacceptable. New equipment may need to be pre-soaked or flushed with adilute hydrofluoric acid solution, or both, to obtain a stable siliconbackground.NOTE 3It is recommended that an auto sampler with tube racks andplastic sample tubes compatible with the ICP-MS be used.7.1.2
24、 Balance to read to 0.01 g intervals or less.7.1.3 Appropriately sized, variable volume pipettes such as1 to 10 mL; 100 to 1200 L; 20 to 300 L; 5 to 100 L usedwith polyethylene pipette tips.7.1.4 Appropriately sized plastic, spouted measuring cylin-ders (for preparing dilute acids).7.1.5 Plastic bea
25、kers, 100 mL size.7.1.6 Low density polyethylene bottles with leak proof lids,various sizes.NOTE 4PFA containers may be used as an alternative and may help toreduce silicon background levels.7.1.7 Polyfluoroalkoxy fluorocarbon plastic (PFA) bottles,various sizes.7.1.8 Polyethylene sample tubes with
26、leak proof lids, 25 mLand 50 mL size.7.1.9 Disposable Glovesimpermeable and powder free toavoid the potential for contamination and to provide protectionagainst toxic and corrosive substances. PVC gloves are suit-able.NOTE 5 The use of glassware must be avoided throughout this methodas interaction w
27、ith acid fluoride solutions will affect the silicon measure-ment.8. Reagents and Materials8.1 The sensitivity of the ICP-MS technique requires the useof ultra high purity reagents in order to be able to obtain lowlevels of detection and satisfactory precision. All the reagentsbelow are ultra high pu
28、rity grade unless otherwise stated.8.1.1 Concentrated nitric acid, specific gravity 1.42, 16 M.8.1.2 Concentrated hydrochloric acid, specific gravity 1.18,11.3 M.8.1.3 Concentrated hydrofluoric acid, 48 % by weight orsimilar concentration.8.1.4 Reagent water conforming to Specification D1193.8.1.5 N
29、itric acid, 0.32 M (200 mL of concentrated nitricacid diluted to 10 L or equivalent ratio).8.1.6 Nitric acid, 2 M (125 mL of concentrated nitric aciddiluted to 1 L or equivalent ratio).8.1.7 Nitric acid, 3 M (188 mL of concentrated nitric aciddiluted to 1 L or equivalent ratio).8.1.8 Hydrochloric ac
30、id, 0.1 M (8.8 mL of concentratedhydrochloric acid diluted to 1 L or equivalent ratio).8.1.9 Two independent 10 000 mg/L silicon standards (onefor calibration, one for sample spiking and Quality Control).8.1.10 Two independent 1000 mg/L boron standards (onefor calibration, one for sample spiking and
31、 Quality Control).8.1.11 Two independent technetium standards (one forcalibration, one for sample spiking and Quality Control).Concentrations at 52.04 Bq/mL (82 g/L) and 63.24 Bq/mL(100 g/L) have proven acceptable but other similar valuesmay be used if precisely known.8.1.12 1000 mg/L indium, scandi
32、um and beryllium stan-dards (used for internal reference solutions).NOTE 6Alternative elements may be used for the internal referencesolution. Care must be taken to ensure consistency between batches ofstandards where the element chosen has more than one naturally occurringisotope.8.1.13 Synthetic P
33、seudo Blank Matrix. 29 mL of 48 % byweight hydrofluoric acid diluted to 1 L or equivalent mixture toproduce a 1.3 % by weight fluoride solution (equivalentfluoride concentration toa4%byweight UF6solution). Storein a PFA bottle and mix thoroughly before use.8.1.14 Bulked Pseudo Blank Matrix. This is
34、syntheticpseudo blank matrix that has passed through the preparationand solid phase extraction process described in paragraphs12.1-12.10, measured and shown to contain very low levels ofC1771 132boron, silicon and technetium. It is used to prepare calibrationstandards and instrument quality control
35、samples.8.1.15 Pre-packed DAAP resin columns, 2 mL, togetherwith reservoirs and end caps as appropriate.NOTE 7New columns may need to be pre-treated before first use toremove trace silicon contamination. Pre-treatment may be carried out bypassing sample material that does not require analysis throug
36、h the column,eluting and regenerating the column as described in Section 12.8.1.16 Argon gas (carrier gas for the ICP-MS), 99.99 %purity.9. Hazards9.1 Adequate laboratory facilities, such as fume hoods andcontrolled ventilation, along with safe techniques, must be usedin this procedure. Extreme care
37、 should be exercised in usinghydrofluoric and other concentrated acids. Use of chemicalresistant gloves and eye protection is recommended. Refer tothe laboratorys health and safety arrangements and otherapplicable guidance for handling chemical and radioactivematerials and for the management of radi
38、oactive, mixed, andhazardous waste.9.2 Hydrofluoric acid is a highly corrosive acid that canseverely burn skin, eyes, and mucous membranes. Hydroflu-oric acid is similar to other acids in that the initial extent of aburn depends on the concentration, the temperature, and theduration of contact with
39、the acid. Hydrofluoric acid differsfrom other acids because the fluoride ion readily penetrates theskin, causing destruction of deep tissue layers. Unlike otheracids that are rapidly neutralized, hydrofluoric acid reactionswith tissue may continue for days if left untreated. Due to theserious conseq
40、uences of hydrofluoric acid burns, prevention ofexposure or injury of personnel is the primary goal. Utilizationof appropriate laboratory controls (hoods) and wearing ad-equate personal protective equipment to protect from skin andeye contact is essential.9.3 The ICP-MS is a source of intense ultra-
41、violet radiationfrom the radio frequency induced plasma. Protection fromradio frequency radiation and UV radiation is provided by theinstrument under normal operation.10. Calibration and Standardization10.1 The standards and blanks described below are pre-pared. The laboratory may choose to prepare
42、different volumesof these materials and at different concentrations where appro-priate to the requirements of the laboratory and the measure-ment to be performed.10.2 Internal Reference Solution (50 g/L In, 100 g/L Scand 500 g/L Be). Add approximately 1.5 L of 0.32 M nitricacid toa2LPFAbottle. Pipet
43、 0.1 mL of 1000 mg/L indiumstandard, 0.2 mL of 1000 mg/L scandium standard and 1.0 mLof 1000 mg/L beryllium standard into the bottle. Fill up to the2 L mark with 0.32 M nitric acid. Mix thoroughly before use.10.3 Boron, Silicon and Technetium Stock Solution, used forcalibration standards (2.5 mg/L B
44、, 100 mg/L Si and 500 ng/L99Tc). Place a labeled 125 mL PFA bottle on to a balance andtare. Add approximately 50 mL of 0.32 M nitric acid to thebottle. Pipet 0.25 mL of 1000 mg/L boron standard, 1.0 mL of10 000 mg/L silicon standard and 0.61 mL of 82 g/Ltechnetium standard solution into the bottle.
45、Make up to 101 g(60.5 g) with 0.32 M nitric acid. Add screw top lid and mixthoroughly.NOTE 8The volume of a technetium standard with a different startingconcentration should be adjusted to give the required final concentrationof 500 ng/L, or any different concentration deemed more appropriate tothe
46、requirements of the laboratory (see 10.1).NOTE 9The density of 0.32 M nitric acid at 20C is taken to be 1.009g/mL.10.4 Boron Silicon and Technetium Blank Calibration Stan-dard. Place a labeled 125 mL PFA bottle on to a balance andtare.Add 101 g (60.5 g) of Bulked Pseudo Blank Matrix to thebottle. Ad
47、d screw top lid and mix thoroughly.10.5 Boron, Silicon and Technetium Calibration Standard 1(10 g/L B, 400 g/L Si and 2.0 ng/L99Tc). Place a labeled 125mL PFA bottle on to a balance and tare. Add approximately 50mL of Bulked Pseudo Blank Matrix to the bottle. Pipet 0.4 mLof Boron, Silicon and Techne
48、tium Stock Solution into thebottle and make up to 101 g (60.5 g) with Bulked PseudoBlank Matrix. Add screw top lid and mix thoroughly.10.6 Boron, Silicon and Technetium Calibration Standard 2(20 g/L B, 800 g/L Si and 4.0 ng/L99Tc). Place a labeled 125mL PFA bottle on to a balance and tare. Add appro
49、ximately 50mL of Bulked Pseudo Blank Matrix to the bottle. Pipet 0.8 mLof Boron, Silicon and Technetium Stock Solution into thebottle and make up to 101 g (60.5 g) with Bulked PseudoBlank Matrix. Add screw top lid and mix thoroughly.10.7 Boron, Silicon and Technetium Calibration Standard 3(50 g/L B, 2.0 mg/L Si and 10 ng/L99Tc). Place a labeled 125mL PFA bottle on to a balance and tare. Add approximately 50mL of Bulked Pseudo Blank Matrix to the bottle. Pipet 2.0 mLof Boron, Silicon and Technetium Stock Solution into thebottle and make up to 101 g (60
